Issue 25, 2021

The pnictogen bond: a quantitative molecular orbital picture


We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A (Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn–Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO–LUMO interactions between the lone pair of A and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.

Graphical abstract: The pnictogen bond: a quantitative molecular orbital picture

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Article information

Article type
10 Apr 2021
03 Jun 2021
First published
04 Jun 2021
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2021,23, 13842-13852

The pnictogen bond: a quantitative molecular orbital picture

L. de Azevedo Santos, T. A. Hamlin, T. C. Ramalho and F. M. Bickelhaupt, Phys. Chem. Chem. Phys., 2021, 23, 13842 DOI: 10.1039/D1CP01571K

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